AU641937B2 - Spreads containing chlorophyll - Google Patents

Abstract

Oil processing for spread manufacture is a complex and expensive process. During the refining process many of the trace components of the original unrefined oil are lost. The invention concerns the use of unrefinined oils to prepare edible emulsions without the necessity of refining. The products according to the invention are characterised as being edible emulsion comprising at least 1ppm chlorophyll on fat phase. Such levels of chlorophyll are found for example in spreads prepared as blends of olive oil and butter.

Description

AUSTRALIA

PATENTS ACT 1952 Form COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE Short Title: Int. Cl: Application Number: Lodged: Complete Specification-Lodged: Accepted: Lapsed: Published: Priority: 4 Related Art: TO BE COMPLETED BY APPLICANT Name of Applicant: UNILEVER PLC Address of Applicant: UNILEVER HOUSE AE REG BLACKFRIARS 22.10 (2) LONDON EC4 ENGLAND T Actual Inventor: Address for Service:, GR FF-PH-HAG ,t I 001 St. Ul da-Road, r- ii" Complete Specification for the invention entitled: SPREADS CONTAINING CHLOROPHYLL.

The following statement is a full description of this invention including the best method of performing it known to me:- S 1,A L 7200 (R) SPREADS CONTAINING CHLOROPHYLL The present invention concerns the technical field of edible spreads.

The present invention relates to edible water-in-oil emulsions containing chlorophyll, particularly to blends comprising butterfat and unrefined vegetable oil' suitable for use as spreads on bread and for kitchen use, and in particular embodiments to spreads containing unrefined olive oil and butterfat.

Manufacture of olive oil for human or animal consumption requires nothing other than expression of the oil from the oil bearing materials and clarification of the oil by filtration. Such a process commonly includes so called cold-pressing and the product is referred to as "virgin olive oil". Commercial olive oil is often a blend of olive oils from a number of different sources, some or much of which may be refined olive oil. Blends 0, of around 10-20%wt virgin olive oil and around 80-90% refined olive oil are available in the marketplace as "olive oil".

*25 Olive oil is described in BAILEY ("Industrial Oil and Fat Products": Wiley, Fourth Edition, Volume 1 page se, 368ff) as unique in that it is used (as a dressing) for it's flavour whereas the other edible oils are refined prior tc use. Many examples of refining processes are given in BAILEY (cit. ultra) as are examples of the offflavour components which are generated on storage of unrefined edible oils.

Unrefined vegetable oils are characterised by the presence of quite large amounts of tocopherols (vitamin E family) and colouring agents other than chlorophylls, especially f-carotenes (closely related to vitamin A).

r 2 L 7200 (R) It is believed that the tocopherols may have some antioxidative activity, and both the vitamin components are reported to have nutritive value. While the carotenoids are moderately resistant to decomposition, chlorophyll is particularly sensitive to the refining process.

Hence although chlorophyll is present in many unrefined vegetable oils it is removed or decomposed during refining.

Olive oil is particularly rich in chlorophyll, which contributes to the characteristic colour of the oil.

The level of chlorophyll in the oil varies with the state of maturation of the olives from which the oil has ,15 been expressed, in quantities ranging from 1-10 mg/kg, with a typical value of around 2.5 mg/kg. Certain other Soils and fats have similar levels of chlorophyll, for example crude soybean and sunflower oils have 0.4-5.0 mg/kg and rapeseed oil may comprise up to 10 mg/kg of chlorophyll.

Refining processes such as are commonly used for edible oils and fats comprise a plurality of steps, such as degumming, neutralising, bleaching and deodorising.

*25 Chlorophyll is particularly sensitive to these refining processes and is normally lost during the degumming and bleaching steps. With soyabean and sunflower oil the level of chlorophyll is lowered during bleaching to below 0.1 mg/kg. Other components such as gossypol, carotenoids and cycloartenol are lost during the refining process. The level of tocopherols is reduced, particularly during deodorisation. As a consequence of these losses manufacturers commonly add back carotenoids and tocopherols to maintain colour, prevent oxidation and for nutritional reasons.

I 3 L 7200 (R) Margarine formulations often contain a proportion of high-melting fat to provide body and structure. These "hardstocks" are obtained by the chemical hydrogenation of liquid oils and as a result of the hydrogenation process contain trans fatty acid residues. Some consumers find the presence of trans fatty acids unacceptable. Chlorophyll is not usually completely bleached in the hydrogenation process, whereas the other colouring agents naturally present in the feedstock (red and yellow pigments) are ether removed or readily reduced during hydrogenati n. As a result of this difference fats containing both chlorophyll and other colouring agents change colour when hydrogenated unless 15 special catalysts (copper chromates) are employed.

Do Most margarine formulations als ,contain emulsifiers.

These are usually sepected from lecithins, saturated monoglycerides and unsaturated mono-glycerides and mixtures of the,same. The presence of these emulsifier additives is unacceptable to some consumers.

There is a general need in the edible spreads industry to find product formulations which have a minimum number 25 of components and in which the components have been subjected to a minimum number of process steps.

We have determined that when particular formulations are employed, the above mentined refining processes are not necessary and unrefined, unhydrogenated, i.e coldpressed, vegetable oils can be used in the manufacture of products which contain no added emulsifier and little orno trans fatty acids.

According to the present invention there is provided an edible emulsion comprising a dispersion of oil and water CHARACTERISED IN THAT at least 0.5 ppm chlorophyll is dispersed in the oil phase.

The presence of chlorophyll in products which contain no trans fat is characteristic of unrefined, unhydrogenated oils. While chlorophyll has previously present in spreads by virtue of the incorporation of particles of vegetable matter, such as parsley as in "beurre a la Maitre d'Hotel", or "beurre a la Chivry", the chlorophyll was not homogeneously distributed in the fat phase of an oil and water emulsion.

Compositions according to the present invention are preferably free of particulate vegetable matter such as herb or leaf fragments.

In preferred embodiments of the invention the concentration of chlorophyll does not exceed 15mg/kg (ppm) on liquid oil content at C-values (hardness at indicated temperature) of preferred embodiments of the invention lie in the range C5: 2500- S* 1000, C10: 2000-750, C15: 1000-200, C20: 100-30.

Typically, the relation between the level of chlorophyll and the proportion of oil liquid at 10°C is such that the chlorophyll content is at least 1 ppm on liquid oil content at 10 0

C.

We have found that the presence of such levels of S 30 chlorophyll in spreads does not influence the colour or organoleptic properties of the product in a negative sense.

Although the products are noticeably greenish in comparative tests, single instance inspection of the 0ee*S 9 9 9 o 9 9 9 9 9 9 1 product does not lead to a "green" response. Preferred ranges for chlorophyll are 1-5 ppm on product.

While it is possible to employ a single vegetable fat as the sole component of a spread, it is preferable to manufacture a spread from a blend of fats so as to achieve the necessary hardness. In particular, we have found that the blends of butterfat and unrefined vegetable -7/

U>^

L 7200 (R) oil give good results. The butterfat may be obtained as anhydrous butterfat and used aS such, but the use of unmodified butter is preferred.

Butterfat is chemically distinct from the vegetable fats and oils. Xn particular, butter contains very little or no chlorophyll, is richer in short chain fatty acids and contains more saturated fat than liquid vegetable oils.

Blend of butterfat and edible oils are softer than butter and generally contain lesser proportions of saturated fats. Many medical authorities recommend that the human diet should contain less saturated fat than is currently the case.

S

.,15 Vegetable fats may be used as alternative hard fats to S. butter. Suitable fats may be obtained by a range of techniques including fractionation, hy rogenation and interesterification or combinations of these techniques.

As was noted above, some consumers find trans fatty acids unacceptable. While trans fatty acids are produced by incomplete hydrogenation of fats, as is commonly performed in the edible fats industry, the trans fatty acids also occur naturally in butter. Gunston Harwood 25 and Padley (the "Lipid Handbook": Chapman and Hall, page 113) report levels of 4-8% trans fatty acids as the elaidate. There are few other sources of tans fats in nature. Where hydrogenated fats are employed care should be taken to minimise the trans fatty acid content.

No emulsifiers, thickeners, colouring agents, preservative or plastifiers are required in the formulations according to the present invention. The butter and unrefined oil are comprise sufficient natural emulsifier components to stabilise the product without further additions.

I

6 L 7200 (R) Preferably the unrefined vegetable oil is olive oil, and the unrefined oil content of the blend lies in the range 5-60%wt on total fat content, most preferably around on total fat content. Some medical authorities consider that olive oil is preferable to other vegetable oils as a foodstuff: in particular due to the high content of mono-unsaturated fatty acid residues and possibly due to the presence of low levels of other nutritional components.

Typical formulations therefore comprise blends of 5-60% extra virgin olive oil and 95-40% butter. In particular embodiments of the invention blends of 25-35% olive oil and 75-65% butter are employed. For butter the contents S, .15 of saturated, mono-unsaturated and poly-unsaturated fatty acids are markedly inclined towards high saturated I fatty acid contents; reported values are 60-70% saturated fatty acids, 25-30% mono-unsaturated fatty acids and up to 5% of poly-unsaturated fatty acids.

Olive oil is particularly rich in mono-unsaturated fatty acids, having a reported content of 65-80% oleic acid.

The remaining major components of olive oil are 4-15% linoleic acid and 9-18% saturated fatty acids. Blends of olive oil and butterfat comprising 30% olive and 25 butterfat would have a typical content as follows: Saturated fatty acids: 48% Mono-unsaturated fatty acids: 42% Poly-unsaturated fatty acids: As an alternative, the vegetable oils can be an unrefined vegetable oil selected from the group comprising; sunflower, soybean, safflower, sesame, mustard, rapeseed, grapeseed and mixtures of the same.

Both high or low oleic oils can be used, where these varieties exist.

7 L 7200 (R) These oils are suitable for inclusion in relatively large amounts. Moreover these'oils comprise relatively large amounts of poly-unsaturated fatty acids, and the resulting blends would generally be richer in polyunsaturated fatty acids than the comparable blends of olive oil and butter. These oils are preferably used at a level of 5-60% on product.

Olive oil comprises some 10% of linoleic acid residues, whereas sunflower oils suitable for cold use comprise some 55-70% linoleic acid, and soybean oils around linoleic acid; consequently a blend of 10% olive with 90% of these two vegetable oils comprises around and preferably more than 50% linoleic acid residues, *15 around 10-35% mono-unsaturated fatty acid residues and relatively low levels of saturated fatty acids. Such a blend may be used in combination with butterfat and/or butter.

Other oils and fats may be incorporated into the formulation. For example chufa (an oil rich in monounsaturated fatty acids), groundnut (aka 'peanut', comprising around 55% oleic acid), walnut, almond, hazelnut and/or other flavored oils can be used as 25 minor amounts of the overall fat blend.

In order that the present invention may be better S" understood the following illustrative examples are given.

8 L 7200 (R)

EXAMPLES

EXAMPLE 1 A spread comprising 10% unrefined olive oil on total fat content was prepared as follows.

3600 grams of Dutch butter and 400 grams of unrefined, cold-pressed olive oil were combined at 4000C and stirred well. No further additives were used. The resulting emulsion was process(d through an ACAB Votator (RTM) sequence with a throughput of 4.0 kg/hr. Details of the line operation conditions were as follows: 15 Al 500rpm Exit temperature 5.9°C C 250rpm Exit temperature 11.2 0

C

SA2 800rpm Exit temperature 4.3°C The product was packed in foil wrappers.

C-values (hardness at indicated temperature) for the product were C5-2350, C10-1950, C15-880, C20-75. The €00 product had a slight green tinge when compared with spreads manufactured from refined oils, but this colour 25 was not particularly noticeable when the product was inspected in isolation. The product had a characteristic olive flavour but was very palatable.

The product gave good results when used as a condiment for pasta, in shallow frying, basting and as a base for sauces.

Products exhibited the following solids fat indices when analysed after stabilization for 1 hr. at ooc and 16 hrs. at o00. The chlorophyll content on product, was 0.9 ppm.

L 7200 (R) Table 1 10 20 30 1 hr. 0°C 44.1 36.5 12.4 2.2 0.0 16 hrs. 0°C 47.9 40.0 12.2 2.7 0.0 EXAMPLE 2 A spread comprising 30% unrefined olive oil on fat phase was prepared as follows.

2800 grams of Dutch butter and 1200 grams of unrefined, cold-pressed olive oil were combined at 40 0 C and stirred ,15 well. No further additives were used. The resulting emulsion was processed through an AAC Votator (RTM) sequence with a throughput of 4.0 kg/hr. Details of the line operation conditions were as follows: Al 600rpm Exit temperature @too A2 600rpm Exit temperature 7.00C C 250rpm Exit temperature 11.9 0

C

The product was packed in tubs.

C-values (hardness at indicated temperature) for the product were C5-1235, C10-790, C15-240, C20-42. As with the above mentioned example the product had a slight 0* green tinge when compared with spreads manufactured from refined oils, but again this colour was not particularly noticeable when the product was inspected in isolation.

The product had a strong and characteristic olive flavour but was very palatable.

Products exhibited the following solids fat indices when analysed after stabilization for 1 hr. at 0°C and 16 hrs. at ooc. The chlorophyll content on product was L 7200 (R) ppm.

Table 2 1 hr. 0 C 16 hrs. 0 C 32.0 36.7 10 25.6 28.7 20 7.9 7.5 30 1.0 1.1 0.0 0.0 EXAMPLE 3 Example 3 was performed with the following compositions; using whole butter as the source of both butterfat and butter serum:

.J

r Sr *r a S 15 a 5045

SOB.

a a *5 S 5000 S B a. a 55 a. a. a

O

be Butterfat Virgin Olive Oil Refined Olive Oil Unrefined soybean Unrefined Sunflower Oil (total fat) Butter serum Salt (NaCl) 25 Potassium Sorbate Water (total aqueous) 80.0 80.0 80.0 80.0 9.20 9.20 10.80 9.20 0.30 0.30 0.30 0.30 0.10 0.10 0.10 0.10 10.40 10.40 8.80 10.40 Example 3B 7 33 20.0 20.0 20.0 20.00 In all cases the waterphase was brought to a pH of 4.2 with 10% w/w citric acid. The butter was melted at 50 0

C

and blended with the oils in a thermostatted, water jacketed tank. Aqueous phases were prepared by dissolving salt and sorbate in boiling water and cooling to 400C, at which temperature the fatty and aqueous phases were mixed. The premix was cooled and worked into a spread by means of a so-called iA-A-C" sequence of Votator (RTM) units using the following processing I U L 7200 (R) conditions; at a throughput of 3.5 kg/hr.

PREMIX Exit temp. 5.0 6.5 13.5 rotation speed: 1000 800 250 coolant temperature -5 -l volume: 150 As with the previous exampl~es the product had a slightly different colour to a conventional spread. However, the products were otherwiso acceptable.

The~ chlorophyll contents of the products were as 15 follows:

C

ass. as

S

S

Cod...

I

S.

5 0 we *5 C 0

S

CC

4e 4

CC.'

3B 0.7 3C 4.0 3D 4.2 Chlorophyll ppm 3.4

C

0044 *Cdq

CC

S

CC

CC

SO

-C S 35 C. A

CS

CC